Selectively lateral growth of silicon oxide thin film

ABSTRACT

Implementations disclosed herein generally relate to methods of forming silicon oxide films. The methods can include performing silylation on the surface of the substrate having terminal hydroxyl groups. The hydroxyl groups on the surface of the substrate are then regenerated using a plasma and H 2 O soak in order to perform an additional silylation. Further methods include catalyzing the exposed surfaces using a Lewis acid, directionally inactivating the exposed first and second surfaces and deposition of a silicon containing layer on the sidewall surfaces. Multiple plasma treatments may be performed to deposit a layer having a desired thickness.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of the Co-pending U.S.patent application Ser. No. 14/984,599, filed on Dec. 30, 2015, whichclaims benefit of U.S. Provisional Patent Application Ser. No.62/113,944 (APPM/22694USL), filed Feb. 9, 2015. Each of theaforementioned patent applications is herein incorporated by reference.

BACKGROUND

Field

Implementations described herein generally relate to semiconductormanufacturing, and, more specifically, to methods of selectively formingsilicon oxide films.

Description of the Related Art

As the semiconductor industry introduces new generations of integratedcircuits (IC's) having higher performance and greater functionality, thedensity of the elements that form those IC's is increased. Withincreased element density, the dimensions, size and spacing between theindividual components or elements is reduced. Increased resolution frompatterning processes is one mechanism for reduction in size and spacingof features on an IC.

Increased resolution can be achieved by altering the intrinsicresolution of the pattern. The intrinsic resolution of a pattern is thefinest spatial detail that a pattern can transfer. The intrinsicresolution is a function of factors such as the wavelength of radiationused and the size of the features in a pattern. Pattern multiplicationprocesses, such as self-aligned double patterning (SADP) andself-aligned quadruple patterning (SAQP), can be used to increase theresulting resolution of a patterning process without changing theintrinsic resolution of exposure tools. Thus, these processes candecrease the number of lithography exposures per layer, which decreasesa significant cost in device fabrication.

Current pattern multiplication is usually achieved by the combination ofseveral deposition and etch steps. Such approach is highly costinefficient, and may create significant integration complexity. Further,as feature sizes becomes smaller

Therefore, there is a need for new methods of controlling feature sizein ICs.

SUMMARY

Implementations described herein generally relate to methods ofselectively depositing silicon oxide layers, such as a selectivedeposition on dielectric surfaces while avoiding deposition on metalsurfaces. The methods generally include performing silylation on thesurfaces having exposed hydroxyl groups. When a surface with OH isexposed to a silylating agent, the agent reacts with OH to form acovalent linkage to a —O—Si(CH₃)₃ group. The hydroxyl groups on thesurface of the substrate are then regenerated using anitrogen-containing plasma and an H₂O soak in order to convert the—O—Si(CH₃)₃ group to a Si—OH group and to perform additionalsilylations. Multiple silylations, plasma treatments, and soaks may beperformed to deposit a layer having a desired thickness.

In one implementation, a method of depositing a silicon oxide film caninclude positioning a substrate in a process chamber, the substratehaving: a first layer; and a second layer disposed over the first layer,the second layer having an exposed second surface and one or morefeatures formed therein, the features creating one or more sidewallsurfaces and an exposed first surface; treating the substrate with acatalyst, the catalyst comprising a Lewis acid, the catalyst formingterminal reactive groups on the exposed first surface, the one or moresidewall surfaces and the exposed second surface; delivering a catalystdeactivator to the substrate, the catalyst deactivator being activatedby a plasma, the substrate being biased such that the catalystdeactivator is received by the exposed first surface and the exposedsecond surface, the terminal reactive groups being maintained on the oneor more sidewall surfaces; and delivering a silanol to the substrate,the silanol depositing a silicon-containing layer on the one or moresidewall surfaces.

In another implementation, a method of depositing a silicon oxide filmcan include positioning a substrate in a process chamber, the substratecomprising a dielectric region having an exposed dielectric surface andone or more features formed therein, the features having sidewalls, theexposed dielectric surface and the sidewalls having terminal hydroxylgroups; and a metal region, the metal region having an exposed surfacewhich is substantially oxygen free; and performing one or moresilylation cycles to deposit a silicon and carbon containing layerselectively on the sidewalls and the exposed dielectric surface, each ofthe silylation cycles comprising performing a silylation on the surfaceof the substrate, the silylation depositing a silicon and carboncontaining layer; exposing the substrate to a nitrogen-containingplasma, the nitrogen-containing plasma displacing at least one carbonwith a nitrogen in the silicon and carbon containing layer; and exposingthe substrate to a water-containing gas to form hydroxyl groups on thesurface of the substrate.

In another implementation, a method of depositing a silicon oxide filmcan include positioning a substrate in a process chamber, the substratehaving: a metal layer comprising copper; and a dielectric layer disposedover the metal layer, the dielectric layer having an exposed dielectricsurface and one or more features formed therein, the features creatingone or more sidewall surfaces and an exposed metal surface; treating thesubstrate with a catalyst, the catalyst comprising a tetramethylaluminum, the catalyst forming a terminal CH₃ group on the exposed metalsurface, the one or more sidewall surfaces and the exposed dielectricsurface; forming a capacitively coupled plasma comprising a catalystdeactivator; delivering the capacitively coupled plasma to thesubstrate, the substrate being biased such that the catalyst deactivatoris received by the exposed metal surface and the exposed dieelctricsurface, the terminal CH₃ groups being maintained on the one or moresidewall surfaces; and delivering a silanol to the substrate, thesilanol depositing a silicon oxide layer on the one or more sidewallsurfaces.

BRIEF DESCRIPTION OF THE DRAWINGS

So that the manner in which the above recited features of the presentdevices and methods can be understood in detail, a more particulardescription of the devices and methods, briefly summarized above, may behad by reference to implementations, some of which are illustrated inthe appended drawings. It is to be noted, however, that the appendeddrawings illustrate only typical implementations of the devices andmethods and are therefore not to be considered limiting of its scope,for the devices and methods may admit to other equally effectiveimplementations.

FIG. 1 is a cross-sectional view of a processing chamber adapted topractice implementations.

FIG. 2 is a flow diagram of method operations for depositing a siliconoxide film, according to one implementation.

FIGS. 3A-3D illustrate a substrate during formation of a silicon oxidefilm, according to one implementation.

FIG. 4 is a flow diagram of method operations for depositing a siliconcarboxide film, according to one implementation.

FIGS. 5A-5E illustrate a substrate during formation of a siliconcarboxide film, according to another implementation.

To facilitate understanding, identical reference numerals have beenused, where possible, to designate identical elements that are common tothe figures. It is contemplated that elements and features of oneimplementation may be beneficially incorporated in other implementationswithout further recitation.

DETAILED DESCRIPTION

Implementations described herein generally relate to methods of formingcarbon-doped oxide films. The methods generally include generatinghydroxyl groups on a surface of the substrate using a plasma, and thenperforming silylation on the surface of the substrate. The hydroxylgroups on the surface of the substrate are then regenerated using aplasma in order to perform an additional silylation. Multiple plasmatreatments and silylations may be performed to deposit a layer having adesired thickness.

FIG. 1 is a cross-sectional view of a processing chamber 100 accordingto one implementation. The processing chamber 100 has a chamber body 102and a chamber lid 104 that couples to the chamber body 102 to define aninterior 150. A substrate support 106 is disposed in the interior 150 ofthe chamber 100. An upper surface 166 of the substrate support 106 and alower surface 168 of the chamber lid 104 define a processing region 108in which a substrate disposed in a substrate contact area 176 on theupper surface 166 of the substrate support 106 is exposed to aprocessing environment.

Substrates enter and exit the processing chamber 100 through a substratepassage or opening 110 in the chamber body 102. In the cross-sectionalview of FIG. 1, the substrate passage or opening 110 is behind thecross-section plane, in the “back” of the chamber 100. The substratesupport 106 is movable along a longitudinal axis of the chamber 100 toposition the substrate support 106 alternately in a substrate handlingposition, with the upper surface 166 of the substrate support 106proximate the opening 110, and a substrate processing position, with theupper surface 166 of the substrate support 106 proximate the lowersurface 168 of the chamber lid 104. In the view of FIG. 1, the substratesupport 106 is shown in the substrate processing position. When thesubstrate support 106 is located in the substrate processing position, adistance between the upper surface 166 of the substrate support 106 andthe lower surface 168 of the chamber lid 104 is about 2 mm to about 8mm. A shaft 172 of the substrate support 106 typically extends throughan opening 120 in a lower wall 170 of the chamber body 102 and couplesto a lift mechanism (not shown) to actuate movement of the substratesupport 106.

A substrate elevator 112 is disposed through the substrate support 106.The substrate elevator 112 has a base 114 that contacts an actuator 116disposed in a lower area of the interior 150 of the chamber 100. Theactuator 116 is supported from the lower wall 170 by a support member118. The actuator 116 may be an annular member, such as a ring, and thesupport member 118 may be an annular protrusion from the actuator 116.The actuator 116, the support member 118, or both may alternately besegmented. For example, either or both may be a segmented annularmember, or the actuator 116 may be a pad, post, or spindle positioned toengage the base 114 of the substrate elevator 112.

The support member 118 maintains the actuator 116 in a substantiallyparallel relation to the upper surface 166 of the substrate support 106.When the substrate support 106 is moved from the processing position tothe substrate handling position, the base 114 of the substrate elevator112 contacts the actuator 116, causing the substrate elevator 112 toprotrude through the upper surface of the substrate support 106 and lifta substrate disposed thereon above the upper surface for access by asubstrate handling robot (not shown) through the opening 110. Only twosubstrate elevators 112 are visible in the view of FIG. 1, but a typicalimplementation will have three or more substrate elevators 112distributed to provide stable stationing for substrate handling.

The chamber lid 104 may be an electrode, and may be coupled to a sourceof RF power 174. If the chamber lid 104 is an electrode, the chamber lid104 will typically include a conductive material. The chamber lid 104may be entirely or substantially made of a conductive material, or maybe coated with a conductive material to any convenient degree. If thechamber lid 104 is used as an electrode, the lower surface 168 of thechamber lid 104 will be conductive to provide RF coupling into theprocessing region 108 proximate the upper surface 166 of the substratesupport 106. In one implementation, the chamber lid 104 is aluminum. Theprocessing chamber 100 is adapted to generate a plasma therein, such asa capacitively coupled plasma.

A gas manifold 124 is coupled to the chamber lid 104 at a port 194.Process gases are delivered to the chamber through a gas line 128. Aplurality of high speed valves 126A-C control flow of gases through thegas line 128 into the chamber 100. The high speed valves may be ALDvalves, and in some implementations may be capable of opening or closingin less than 1 second, and in some cases less than 0.25 seconds. Aprecursor line 130 is coupled to one of the high speed valves 126A-C.The other high speed valves may be used to join other precursor lines,not visible in FIG. 1, to deliver gases through the gas line 128.Operation of the high speed valves enables fast switch of gas flows asneeded for chamber operations, such as ALD deposition cycles.

The chamber lid 104 has a gas inlet 122 located in a peripheral regionof the chamber lid 104 and in fluid communication with the port 194 andthe gas manifold 124. The gas inlet 122 may be located outside thesubstrate contact area 176 of the substrate support 106. An edge ring136 is disposed around a peripheral region of the substrate support 106.The edge ring 136 may be an annular member having an inner dimension andan outer dimension. The inner dimension of the edge ring 136 may besubstantially the same as a dimension of the substrate contact area 176such that a substrate disposed on the substrate support nests inside theedge ring 136, as shown in FIG. 1. The inner dimension of the edge ring136 may also be larger than the dimension of the substrate contact area176. The inner dimension of the edge ring 136 may also be smaller thanthe substrate contact area 176 so that a portion of the edge ring 136extends over an edge of the substrate. The edge ring 136 of FIG. 1 restson the substrate support 106 when the substrate support 106 is in theprocessing position. Thus, the substrate support 106 also supports theedge ring 136 when in the processing position.

A pumping plenum 132 is located in a side wall 178 of the chamber body102 proximate the processing position of the substrate support 106. Thepumping plenum 132 is an annular passage around the processing region108 where processing gases are evacuated from the processing region 108.A liner 134 separates the pumping plenum 132 from the processing region108. The liner 134 has an opening 180 that allows process gases to flowfrom the processing region 108 into the pumping plenum 132. The opening180 is typically located below the upper surface 166 of the substratesupport 106 when the substrate support 106 is in the processingposition.

FIG. 2 is a flow diagram of a method 200 for depositing a carbon-dopedoxide film, according to one implementation. The method 200 includespositioning a substrate in a process chamber, the substrate having afirst layer; and a second layer disposed over the first layer, thesecond layer having an exposed second surface and one or more featuresformed therein, the features creating one or more sidewall surfaces andan exposed first surface, at element 202; treating the substrate with acatalyst, the catalyst comprising a Lewis acid, the catalyst formingterminal reactive groups on the exposed first surface, the one or moresidewall surfaces and the exposed second surface, at 204; delivering acatalyst deactivator to the substrate, the catalyst deactivator beingactivated by a plasma, the substrate being biased such that the catalystdeactivator is received by the exposed first surface and the exposedsecond surface, the terminal reactive groups being maintained on the oneor more sidewall surfaces, at 206; and delivering a silanol to thesubstrate, the silanol depositing a silicon-containing layer on the oneor more sidewall surfaces, at 208. FIGS. 3A-3D illustrate a substrateduring formation of a silicon oxide film, according to oneimplementation. To facilitate explanation of implementations disclosedherein, FIG. 2 and FIGS. 3A-3D will be explained in conjunction.

The method 200 begins by positioning a substrate in a process chamber,the substrate having a first layer; and a second layer disposed over thefirst layer, the second layer having an exposed second surface and oneor more features formed therein, the features creating one or moresidewall surfaces and an exposed first surface, at 202. In element 202,a device 300, shown in FIG. 3A, is positioned in a processing chamber,such as processing chamber 100 shown in FIG. 1. The device 300 comprisesa substrate 302. The substrate 302 may be, for example, a silicon waferhaving a silicon oxide layer or carbon-doped silicon oxide layerthereon. The substrate 302, as illustrated, includes a first layer 304.The first layer 304 can be a metal layer, such as a layer containingcopper. A second layer 306 can be formed above the first layer 304. Thesecond layer 306 can be a dielectric layer, such as a silicon oxidelayer. As shown, the second layer 306 has an exposed second surface 310and one or more features 307 formed therein. The one or more features307 have a sidewall surface 309 and extend down to an exposed firstsurface 308.

Positioned in the process chamber, the substrate is treated with acatalyst, the catalyst comprising a Lewis acid, at 204. The Lewis acidcan be an organo compound, such as an organoaluminum compound, anorganoiron compound, an organotitanium compound, an organozinc compound,or combinations thereof. In one implementation, the Lewis acid is eithertrimethylaluminum (TMA), tetramethyl titanium, tetramethyl zinc orcombinations thereof. The Lewis acid can further be a halogen containingcompound, such as AlCl₃, FeCl₃, TiCl₄, ZnCl₄ or combinations thereof.The Lewis acid reacts with the exposed surfaces, such as the exposedfirst surface 308, the one or more sidewall surfaces 309 and the exposedsecond surface 310, creating a layer 312 having terminal reactivegroups, as shown in FIG. 3B. Using the above Lewis acids, the terminalreactive groups of the layer 312 can be organic groups, such as a methylgroup, or halogen groups, such as chlorine groups.

A catalyst deactivator can then be delivered to the substrate, thecatalyst deactivator being activated by a plasma, at 206. The catalystdeactivator can be a gas such as O₂, N₂, NH₃, H₂, H₂O, He, Ar, orcombinations thereof. The plasma can be a capacitively coupled plasma.The plasma should have an energy level such that the catalystdeactivator is primarily ionized without creating radicals. After thelayer 312 is exposed to the catalyst deactivator and assuming one of thespecifically named Lewis Acids above, the —CH3 or —Cl bond is broken anda non-reactive species is substituted, shown as layer 314 of FIG. 3C.For example, when the catalyst deactivator is O₂ or H₂O, the terminalreactive group is substituted with an —OH group. The substrate is biasedsuch that the catalyst deactivator is received by the exposed firstsurface 308 and the exposed second surface 310, without being receivedby the sidewall surfaces 309. Thus, the terminal reactive groups aremaintained on the sidewall surfaces 309.

Once the exposed first surface 308 and the exposed second surface 310are treated with the catalyst deactivator, a silanol is delivered to thesubstrate, the silanol depositing a silicon-containing layer 316 on theone or more sidewall surfaces, at 208. The silanol can be any compoundhaving the general formula Si(OR)₃OH, where the R group being ahydrocarbon. In one example, the silanol is tris-(tert-butoxy)silanol,tris-(tert-pentoxy)silanol, or derivatives thereof. The silanol isdelivered to the surface of the device 300, where it reacts with theremaining terminal reactive groups of the layer 312 as formed on thesidewall surfaces 309, shown in FIG. 3D.

Depending on the exposure time and concentration, the growth thicknesscan be up to about 200 A on the sidewall surfaces 309. By repeatingelements 204, 206 and 208, is it possible to grow films thicker than 200Å. Advantageously, the growth thickness on surfaces with deactivatedcatalyst (e.g., the exposed first surface 308 and the exposed secondsurface 310) is not measurable. Thus, selective growth can be achievedon the sidewall surfaces 309 without detectable growth on the exposedfirst surface 308 or the exposed second surface 310. This selectivegrowth allows for the creation of smaller features useful for continuedminiaturization of IC devices.

FIG. 4 is a flow diagram of method 400 for depositing a siliconcarboxide film, according to one implementation. The method 400 includespositioning a substrate in a process chamber, the substrate comprising adielectric region having an exposed dielectric surface and one or morefeatures formed therein, the features having sidewalls, the exposeddielectric surface and the sidewalls having terminal OH groups; and ametal region, the metal region having an exposed surface which issubstantially oxygen free, at 402; and performing one or more silylationcycles to deposit a silicon and carbon containing layer selectively onthe sidewalls and the exposed dielectric surface, each of the silylationcycles comprising: performing a silylation on the surface of thesubstrate, the silylation depositing a silicon and carbon containinglayer, at 404; exposing the substrate to a nitrogen-containing plasma,the nitrogen-containing plasma displacing at least one carbon with anitrogen in the silicon and carbon containing layer, at 406; andexposing the substrate to a water-containing gas to form hydroxyl groupson the surface of the substrate, at 408. FIGS. 5A-5E illustrate asubstrate during formation of a silicon carboxide, according to oneimplementation. To facilitate explanation of implementations disclosedherein, FIG. 4 and FIGS. 5A-5E will be explained in conjunction.

The method 400 begins by positioning a substrate in a process chamber,the substrate comprising a dielectric region having an exposeddielectric surface and one or more features formed therein, the featureshaving sidewalls, the exposed dielectric surface and the sidewallshaving terminal OH groups; and a metal region, the metal region havingan exposed first surface 508 which is substantially oxygen free, at 402.In element 402, a device 500, shown in FIG. 5A, is positioned in aprocessing chamber, such as processing chamber 100 shown in FIG. 1. Thedevice 500 comprises a substrate 502. The substrate 502 may be, forexample, a silicon wafer having a silicon oxide layer or carbon-dopedsilicon oxide layer thereon. The substrate 502, as illustrated, includesa first layer 504. The first layer 504 can be a metal layer, such as alayer containing copper. A second layer 506 can be formed above thefirst layer 504. The second layer 506 can be a dielectric layer, such asa silicon oxide layer. As shown, the second layer 506 has an exposedsecond surface 510 and one or more features 507 formed therein. The oneor more features 507 have a sidewall surface 509 and extend down to anexposed first surface 508. The exposed first surface 508 has a terminalnon-reactive species 522, shown here as a hydrogen. The exposed secondsurface 510 and the sidewall surface 509 have terminal hydroxyl groups520.

With the substrate positioned, a silylation is performed on the surfaceof the substrate, the silylation depositing a silicon and carboncontaining layer, at 404. A silylation reaction is performed by exposingthe device 300 to a silylating agent, such as(dimethylamino)trimethylsilane (DMATMS), bis(dimethylamino)dimethylsilane or combinations thereof. The silylation results in thesubstitution of a hydrogen from the hydroxyl group 520 with atrimethylsilyl pendant group 524, as illustrated in FIG. 5C. Thesilylation reaction adds a monolayer of trimethylsilyl groups to thesidewall surfaces 509 and the exposed second surface 510 of the device500. The reaction results in the formation of a silicon oxide layerhaving some carbon incorporated therein due to the presence of themethyl groups of the trimethylsilane, and thus, a silicon carboxidelayer is formed. Using the silylation reaction described above, discretemonolayers of silicon carboxide can be formed, allowing for thereproducible deposition of relatively thin layers on a substrate.

In one example, the substrate is maintained at a temperature within arange of about 25 degrees Celsius to about 400 degrees Celsius, such asabout 75 degrees Celsius. The pressure is maintained within a range ofabout 100 m Torr to about 760 Torr, such as 6 Torr. The silylating agentis carried by an inert gas provided at a flow rate of about 0.1 to about4.0 standard liters/min (slm), such as about 2 slm. The inert gas may beone or more of helium, argon, or diatomic nitrogen. The silylating agentis provided at a rate of about 0.1 gram/min to about 4.0 gram/min. Thesubstrate may be exposed to the silylating agent for about 5 to about300 seconds, such as about 60 seconds.

It is to be noted that silylation reaction consumes the hydroxyl groupspresent in the second layer 506, in implementations such as thedielectric layer, and thus, eventually, further silylation does notoccur. To facilitate further silylation, thus increasing the thicknessof the film formed on the substrate 502, the second layer 506 is treatedto induce the formation of additional hydroxyl groups thereon (e.g.,regenerated).

Once the silylation reaction is complete, the substrate is exposed to anitrogen-containing plasma, the nitrogen-containing plasma displacing atleast one carbon with a nitrogen in the silicon and carbon containinglayer, at 406. The plasma treatment includes exposing the substrate 330to a nitrogen-containing plasma, such as a plasma formed from ammonia.The plasma treatment facilitates the formation of hydroxyl groups bybreaking some of the silicon-methyl bonds, displacing the terminalmethyl group 526 with an amine group 528 as shown in FIG. 5D.

In one example, NH₃ gas may be provided to the chamber at a flow ratebetween about 100 sccm and about 5000 sccm, such as about 150 sccm, andapplying 50 watts RF power to generate a plasma. In another example, RFpower may be between about 10 Watts and about 1000 Watts, such as 60Watts. The substrate may be maintained at a temperature of about 200degrees Celsius, and the chamber pressure may be about 3 Torr. An inertgas, such as N₂, may be provided to the chamber at a flow rate of about100 to about 30000 sccm, such as 27000 sccm. The substrate may bemaintained at a temperature of about 25-400 degrees Celsius, such asabout 200 degrees. The pressure may be maintained within a range ofabout 1 Torr to about 10 Torr, such as 4.2 Torr. The exposure time maybe within a range of about 1 second to about 60 seconds, such as 4-10seconds.

Next, the substrate is exposed to a water-containing gas to formhydroxyl groups on the surface of the substrate, at 408. The substrate502 is exposed to a water-containing gas to facilitate formation ofhydroxyl groups 530 by displacing the amine groups 528 in the pendantgroup 524, as shown in FIG. 5E. The water-containing gas may includesteam or water vapor produced using a water vapor generator (WVG). Inone example, the flow rate of the water vapor gas may be about 1 sccm toabout 1000 sccm, such as about 10 sccm.

Undesirable water molecules, which may present on the surface of thesubstrate 302 after element 408, are desorbed and debonded by reducingthe pressure within the processing chamber and/or by increasing thetemperature within the process chamber. The volatile components may thenbe exhausted from the processing chamber.

Benefits of the implementations generally include the reproducible andselective deposition of silicon oxide films having relatively smallthicknesses, such as less than about 100 angstroms or less than about 10angstroms. The silicon oxide layers can be deposited via Lewis acidcatalyzed silanol deposition. Selectivity can be controlled by biasedinactivation of selected surfaces. In further implementations, thesilicon oxide layers can be deposited via silylation by regenerating thesurface of the substrate with a plasma and water treatment. Silylationallows for accurate layer-by-layer deposition, thus facilitating theformation of very thin layers having exact thicknesses.

While the foregoing is directed to implementations of the application,other and further implementations may be devised without departing fromthe basic scope thereof, and the scope thereof is determined by theclaims that follow.

We claim:
 1. A method of depositing a silicon oxide film, sequentiallycomprising: positioning a substrate in a process chamber, the substratecomprising: a dielectric region having an exposed dielectric surface andone or more features formed therein, the features having sidewalls, theexposed dielectric surface and the sidewalls having terminal hydroxylgroups; and a metal region, the metal region having an exposed surfacewhich is substantially oxygen free; and performing one or moresilylation cycles to deposit a silicon and carbon containing layerselectively on the sidewalls and the exposed dielectric surface, each ofthe silylation cycles comprising: performing a silylation on the surfaceof the substrate, the silylation depositing a silicon and carboncontaining layer; exposing the substrate to a nitrogen-containingplasma, the nitrogen-containing plasma displacing at least one carbonwith a nitrogen in the silicon and carbon containing layer; and exposingthe substrate to a water-containing gas to form hydroxyl groups on thesurface of the substrate.
 2. The method of claim 1, wherein thesilylation cycles further comprise debonding water molecules from thesurface of the substrate.
 3. The method of claim 1, wherein exposing asubstrate to a nitrogen-containing plasma is formed from a gascomprising ammonia.
 4. The method of claim 1, wherein thewater-containing gas is formed using a water vapor generator.
 5. Themethod of claim 1, wherein performing a silylation on the surface of thesubstrate includes exposing the substrate to(dimethylamino)trimethylsilane, bis(dimethylamino) dimethylsilane orcombinations thereof.
 6. The method of claim 1, wherein the one or moresilylation cycles are performed for about 1 cycle to about 20 cycles. 7.The method of claim 1, wherein the dielectric region comprises siliconoxide and the metal region comprises copper.
 8. The method of claim 1,wherein the silylation cycle deposits a silicon carboxide layer.
 9. Amethod of processing a substrate, comprising: (a) conformally forming acatalyst layer on an exposed surface of a layer formed over a substrate,wherein the catalyst layer comprises trimethylaluminum (TMA); (b)exposing the substrate to a plasma formed from a catalyst deactivatorgas, wherein the catalyst deactivator gas comprises O₂, N₂, NH₃, H₂,H₂O, He, Ar, or any combination thereof; (c) exposing the substrate to asilanol to form a material layer on the substrate; and (d) repeating (a)to (c) until a desired thickness of the material layer is achieved. 10.The method of claim 9, wherein the silanol is a compound having thegeneral formula Si(OR)₃OH, the R group being a hydrocarbon.
 11. Themethod of claim 10, wherein the silanol is tris-(tert-butoxy)silanol,tris-(tert-pentoxy)silanol, or derivatives thereof.
 12. The method ofclaim 9, wherein the material layer is silicon oxide.
 13. The method ofclaim 9, wherein the catalyst deactivator gas is O₂ or H₂O.
 14. Themethod of claim 9, wherein the substrate is biased during the process.15. The method of claim 9, wherein the layer is a dielectric layer. 16.The method of claim 9, wherein the material layer is formed on sidewallsof a patterned feature formed in the layer.